Side chain halogenated alkyl phenyl carbamates

ABSTRACT

ALKYL PHENYL CARBAMATES CONTAINING A HALOGENATED SIDE CHAIN ARE USEFUL AS PESTICIDES. SUCH PRODUCTS, FOR EXAMPLE, A,A&#39;&#39;-DICHLORO-3,5-XYLENYL N-METHYL CARBAMATE ARE PREPARED BY REACTING THE CORRESPONDING HALOFORMATES WITH AN ALKYLAMINE.

United States Patent 3,825,582 SIDE CHAIN HALOGENATED ALKYL PHENYL CARBAMATES Edward D. Weil, Hastings-on-Hudson, N.Y., assignor to Hooker Chemical Corporation, Niagara Falls, NY. No Drawing. Application Nov. 7, 1968, Ser. No. 816,426, a now Patent No. 3,651,129, which is a division of application Ser. No. 305,509, Aug. 29, 1963, now Patent No. 3,420,868. Divided and this application June 14,

1971, Ser. No. 153,050

Int. Cl. C07c 125/06 US. Cl. 260-471 C 7 Claims ABSTRACT OF THE DISCLOSURE Alkyl phenyl carbamates containing a halogenated side chain are useful as pesticides. Such products, for example, a,u-dichloro-3,5-xylenyl N-methyl carbamate are prepared by reacting the corresponding haloformates with an alkylamine.

This application is a division of copending application Ser. No. 816,426 which was filed Nov. 7, 1968, now US. 3,651,129, which was a division of parent application Ser. No. 305,509 which was filed Aug. 29, 1963, now US. Pat. 3,420,868 which was patented on Jan. 7, 1969'.

This invention relates to new compositions of matter and to processes for makng them. More specifically, the invention relates to a new class of compounds designated as side chain halogenated alkylphenyl haloformates, O-(alkylaryl)carbamate esters possessing reactive bromine or chlorine atoms on the side chain, which may be derived from the haloformates, and to processes for the preparation thereof.

The haloformate compounds of such compositions of the present invention find utility as pesticides, pesticide intermediates, polymer intermediates, and chemical intermediates which are especially useful for the preparation of side chain halogenated phenols and side chain halogenated phenyl carbamates, carbonates, and other esters.

It is an object of the haloformate aspect of the invention to make available difunctional and higher functional monomeric compounds which, by replacement of two or more reactive halogen atoms by means of a difunctional or higher polyfunctional nucleophilic reagent, will yield useful polymers.

It is a further object to produce compounds which have biocidal and cytostatic activity, for use in pest control and growth retardation of living matter.

Another object is to make available chemical intermediates which can readily be converted to side chain halogenated phenols and their derivatives which have not hitherto been available.

It is still a further object to make chemical intermediates which, by reaction with ammonia, primary amines, or secondary amines, yield pesticidal carbamates, and which, by reaction with alcohols, yield pesticidal carbonates.

It is another object of the present invention to make available a series of versatile chemical intermediates capable of reaction with a great variety of nucleophilic reagents without destruction of the carbamate linkage, and thus giving access to many series of new and useful carbamate derivatives not otherwise available.

A further object of the invention is to make available a series of new carbamates having diverse pesticidal, biocidal and bio-regulatory activity per se.

Another object is to make available convenient processes for manufacture of such compounds.

These and other objects of the invention will become apparent from a further reading of this specification.

ice

The novel compounds of the present invention are wherein the substituents:

l. X and X are halogens of atomic weight between 38 and 81;

2. A is an alkyl radical, preferably of from 1 to about 6 carbon atoms;

. b is from 0 to (S -p), inclusive; c is from 0 to (5'pb), inclusive; m is from 1 to -20; n is from 1 to 2,,, .pisfromltoS;

8. q is equal to the remaining number of valences on the radical C H X 9. Y is selected from the group consisting of (a) halogens of atomic weight between 34 and 81 (b) the radical represented by the formula wherein Z and Z' are selected from the group consisting of hydrogen, hydrocarbyl, hydrocarbyl substituted by hydroxy, halogen, nitro, and may be conjoined by a carbon-to-carbon bond or by an imino-, sulfur or oxygen and (c) the radical represented by the formula QR wherein Q is an element of Group VI of the Periodic Table having an atomic weight between 15 and 33 and R is selected from the group consisting of alkyl, haloalkyl, phenyl, nitrated phenyl, and dialkoxythiophenylthio.

By the term hydrocarbyl is meant the radical obtained by removal of one hydrogen atom from a hydrocarbon and thus encompasses alkyl, alkenyl, aryl, cycloalkyl, cycloalkenyl, and arylalkyl.

The novel side chain halogenated alkylphenyl haloformate compounds of the present invention are represented by the following formula:

wherein the substituents:

1. X, X, X" are halogens of atomic weight between 34 and 81;

2. A is an alkyl substituent, preferably of from 1 to about 6 carbon atoms;

. b is from 0 to '(5-p) inclusive;

c is from 0 to (5-p-b) inclusive;

m is from 1 to about 20;

n is from 1 to 2 p is from 1 to 5; and

q is equal to the remaining number of valences on the group C H X The term alky is intended to encompass cycloalkyl and alkyls substituted by non-interfering substituents. The C H X groups may also be joined to the benzene ring at the adjacent carbon atom of said benzene ring, thus forming a cycloaliphatic ring fused to the benzene ring. The preferred halogenated alkylphenyl haloformates of the invention for reasons of cost are those wherein the substituent:

1. X" is chlorine,

2. n is from 1 to 4, inclusive,

w ave- 3. p is from 1 to 2, inclusive; and

4. c is 0, where more than 1 halogen atom isattached to any single carbon atom on the group C H X A number of O-aryl carbamates have been known which have halogen atoms directly on the aromatic ring. However, such compounds are of no value as chemical intermediates to produce new carbamates, since the ring halogen atoms are inert and cannot be replaced, at least not without degradation of the carbamate linkage.

More specifically, the novel side chain halogenated alkylphenyl carbamates of the invention are represented by the formula:

O i JNZ Z m u n) 1:

wherein the substituent:

1. X and X are halogen of atomic weight from 34 to 81;

2. m is an integer from 1 to about 20;

3. p is an integer from 1 to 5;

4. b is an integer from 0 to (5-p) inclusive;

5. c is an integer from p to (5pb), inclusive;

6. q equals the remaining valences of the group m q n;

7. A is an alkyl substituent; and

8. Z and Z are radicals selected from the group consisting of hydrogen, hydrocarbyl, hydrocarbyl substituted by hydroxy, halogen or nitro, and where both Z and Z may be conjoined by a carbon-to-carbon bond or by an imino, sulfur, or oxygen bridge. The C H X group may optionally be joined to the benzene ring at two adjacent carbon atoms of the benzene ring, thus forming a cycloaliphatic ring fused to the benzene ring.

The preferred embodiments for reasons of cost and efiicacy are those in which n is an integer from 1 to 4, p is an integer from 1 to 2 inclusive, c is 0, where more than 1 halogen atom is attached to any single carbon atom of the group C H X and Z and Z when individual radicals represent a member of the class comprising hydrogen, hydrocarboyl, hydroxy substituted hydrocarbyl, halogensubstituted hydrocarbyl and nitro-substituted hydrocarbyl and when said Z and Z radicals are joined, they represent together with the nitrogen atom to which they are attached, a heterocyclic radical selected from the group consisting of piperidyl, morpholinyl and l-aziridinyl.

There are preferred subgroups, each of which has its particular area of greatest utility. In the present invention, several such carbamate subgroups (chosen on the basis of utility) may be described:

( a)a C- (a) Compounds of the preferred group as described above, wherein Z and Z are chosen from hydrogen and lower alkyl (1 to 5 carbons), or wherein NZZ' represents aziridinyl or l-morpholinyl, have the highest degree of nematocidal and insecticidal activity, as well as the greatest utility as insecticide intermediates. Of this group, the most active per se are those wherein Z is methyl, Z is hydrogen, b is zero, p is an integer from 1 to 2, m is an integer from 1 to about 6, n is an integer from 1 to 4, A is a lower alkyl( having up to 6 carbon atoms), and at least one position ortho to the ester side chain is unsubstituted.

(b) Compounds of the preferred group as described above wherein Z is hydrogen and Z is phenyl, halogenated phenyl, nitrophenyl, and naphthyl, are most active as antimicrobial agents, and are also useful against higher plant organisms.

Viewed from the alternative standpoint of low cost, ease of synthesis and superior yield, those compounds within the scope of the invention wherein C H X represents CH X, CHX or CX are especially advantageous since methylphenyl haloformates are available inexpensively and the methyl side chain (having only a single carbon) does not permit position isomerism in the halogenation. Also advantageous for the same reasons are those compounds wherein C H X represent a CH CHXCH X group in the ortho position to the ester linkage; this group is produced in excellent yield from readily available o-allylphenyl haloformates by the addition of halogen to the allyl group under the conditions of the process of the invention.

Illustrative examples of the (C H X grouping include chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, bromoethyl, dibromoethyl, 1- chloroethyl, 2-chloroethyl, 1,1-dichloropropyl 1,2-dichl0- roproyl, 1,2,3-trichloropropyl, 2,3-dichloropropyl, 2,3-dibromopropyl, dichlorobutyl, chloroisobutyl, chloro-secbutyl, l-chlorocyclohexyl, 2,3-dichlorocyclopentyl, trichlorooctyl, chlorooctadecyl, chloreicosyl, dichloropentadecyl, tetrachloropentadecyl, chlorocyclooctyl, b-romocyclooctyl, chlorocyclobutyl, bromocyclobutyl, and the like. Where p is greater than 0, the several (C H X groups may differ from one another, as may the several X groups and/ or X groups, when b and/ or c are greater than 1.

Among the alkyl substituents which generally contain from 1 to about 20 carbon atoms are methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, isobutyl, tert-butyl, amyl, isoamyl, sec-amyl, hexyl, l-ethylbutyl, eicosyl, and the like. The preferred alkyl groups contain from 1 to about 6 carbon atoms.

Illustrative examples of the halogenated alkylphenyl haloformate compounds included in the present invention are:

O-GOCl ClCHr- O-OOCl CH3- O-COCI CHzCl C (CH )3 CH CH2 G1 Cl Br C1- OCOCl O-COCl Br- 0-COBr Cl CHC12 CHBrg Br OHIBY OCOCI OCOCI CHC1: OCOCI CHCla CC1a- 001a CCIa O1 Several subgroups may be distinguished among the halformates of the invention. Those compounds wherein m is 1 and n is 1 have the reactive benzyl-type halogen atom, and thus are especially useful as reactive intermediates toward nucleophiles and as polymer intermediates. Where there are more than One such -CH X group, the compounds are polyfunctional alkylating agents. Where two -CH X groups are adjacent 0n the ring, the compounds are intermediates for heterocyclic syntheses.

The compounds having -CHX groups are useful intermediates for hydrolysis to aldehydes. The compounds having CX groups are useful intermediates for hydrolysis to carboxylic acids. The compounds having side chains are generally more stable halogen and are also useful for synthesis of long-lasting pesticides. The compounds having CHX groups can be reacted with amines and then with mercaptides to make a,a-bis(hydrocarbylthio)methylphenyl carbamate insecticides.

' Representative examples of carbamates within the scope of the invention include the following:

a-bromo-o-cresyl carbamate a,u-dichl0r0-5-bromo-o-cresyl N-methylcarbamate m-(tetrachloropentadecyl) phenyl N-methylcarbamate u,fi,fl,fi-tetrachloro-m-isopropylphenyl N-methyl carbamate a-chloro-o-eieosylphenyl N-methylcarbamate a,a,3,4, 5,6-hexachloro-o-cresyl N-cyclopentylcarbarnate 4 (chloromethyl)-2,3,5, 6-tetramethylphenyl N,N-dimethylcarbamate a,a-dichloro-2,4-xylenyl N,N-di(2-hydroxyethyl) car-bamate penta(chloromethyl) phenyl N,N-di(2-chl0roethyl) carbamate a,a-dichloro-o-cresyl N-naphthylcarbamate a,3,4-trichloro-0-cresyl N-(p-nitrophenyl) carbamate a,a,a,4,6-pentachl0ro-o-cresyl N(3,4-dich1or0phenyl) carbamate HCICHQ OZQHflcHiCl CICH:

I H3l I 0m 0n, CHBr-CHBr Cl CHa-CH: CH:--CH1 omcnolcmol 111012 00001 C 00 001 ChCH- 00001 0n, CHzCHClCHCl 01202! 03012 CH 01 E 3 0100-0 3 0100-0 6 C-CH: H

CHOlCHaOl 01101 00001 CHCl C--CH: C

0 ClzCHClCHzCl E H 0 011.01 011, 2

a,u,a-tribromo-p-cresyl N-propargylcarbamate '2-*(2,3-dichl0r0pyl) phenyl thiomorpholine-N-carboxylate a,a-dichloro-3,S-xylenyl piperazine-N-carboxylate a,a-dibromo-o-cresyl N-'('2-chl0ro-5-cyclooctenyl) carbamate a,u',4,6-tetrachloro-2,'3-xylenyl N,N-dially1carbamate u-chlor0-2-cycl0hexylphenyl N-benzylcarbamate bis(a-chloro-p-cresyl) ethylene-N,'N'-dicarboxylate 2-bromo'-4-'(chloromethyl)-6-nonylphenyl piperidine-N- carboxylate a,u,a-trichl0ro-m-cresyl pentamethyleneimine-N-carboxylate' 2-('2,3-dibrom0propy1)-o-cresyl N-methylcarbamate 2,4-bis(2,3-dichlor0butyl)-m-cresyl 'N-l-anthracylcarbamate as well as fused ring compounds such as:

and the like. Further examples are given hereinafter.

Novel compounds of the present invention may be prepared by the halogenation of the corresponding haloformates of the formula in which R is a saturated or olefinic hydrocarbyl radical of the same carbon skeleton as the C H X group to be produced, and X, A, m and c are as defined herein, and Y is a halogen atom of atomic weight between 34 and 81, utilizing in said halogenation about It molar equivalents of the halogenating agent under suitable conditions described below, followed by isolation of the desired haloformate or further reaction of said haloformate, with an amine of the formula 'H'NZZ' wherein Z and Z are as defined herein.

Where R is a saturated group, a molar equivalent of a halogenating agent will be sufficient to remove one gramatom of hydrogen and replace said gram-atom of hydrogen with one X gram-atom. Where R is an olefinic group, a molar equivalent of halogenating agent will be that which introduces one gram-atom of halogen (X). Obviously, when R is olefinic, the first halogen atoms will enter two at a time by addition to the double bond and n will have minimum value of 2.

By halogenating agent is meant the free halogen or any equivalent halogenating agent capable of yielding up its halogen under free radical reaction conditions, for example, sulfuryl chloride, phosphorus pentachloride, phosphorus pentabromide, N-chloroand N-bromo amines and amides such as N-chlorobenzamide, N-bromosuccinimide, N,N-dibromodimethylhydantoin, N,N'-dichlorodimethylhydantoin, N-chlorinated isocyanuric acids, and N, N-dichlorop-toluenesulfonamide and the like. The preferred halogenating agents are chlorine, bromine, and sulfuryl chloride.

Suitable conditions for the reaction include those in which free halogen radicals are generated. For example, in the practice of the process of the invention, temperatures in the range of from about -40 degrees centigrade to 200 degrees centigrade, preferably 20 degrees centigrade to 170 degrees centigrade, are employed, also free radical chain initiators are desirably present, including actinic light, diacyl peroxides such as benzoyl peroxide, acetyl peroxide, alkyl or arylalkyl peroxides and hydroperoxides such as cumene hydroperoxide and acetone peroxide, peracids such as perbenzoic acid, m-chloroperbenzoic acid, perphthalic acid, and peracetic acid and azo compounds such as azobis-isobutyronitrile. These agents may be used separately or together. Generally, such catalysts are used at 0.001 percent to percent concentration. Further adjuvants may be used to suppress ring chlorination, although the process of the invention does not require them. In general, these suppressing agents are believed to act by complexing with, and thus deactivating, traces of Lewis acids, such as ferric chloride, which would otherwise catalyze ring substitution; however, applicants do not wish to be bound by this theory. Such adjuvants include phosphorus chlorides, organic phosphates or phosphites such as triphenyl phosphate or phosphite, amides such as urea, acetamide and benzamide, and polyols such as glycerol, sorbitol and mannitol. The halogenation may conveniently be efiected without a solvent, although halogen resistant solvents such as carbon tetrachloride and chlorobenzenes may be used if desired. Atmospheric pressure is conveniently employed, but subor super-atmospheric pressures are also operable. While the stoichiometry of the process calls for molar equivalents of halogenating agent, a moderate deficiency or excess may be employed, and the desired product may be separated from lower and higher halogenated products by distillation, crystallization, or other means.

That the halogenation process of the invention succeeds is especially surprising in view of the usual reactivity of the phenyl ring when it bears an oxygen atom. Unpredictably, it seems that placing a COCl group on the phenolic hydroxyl group has so deactivated the ring toward halogen substitution or addition as to permit side chain halogenation.

Another process for preparing the haloformate compounds of the invention where the mentioned haloalkyl side chains are oand/ or phalomethyl is by the reaction of phenyl haloformate having at least one unsubstituted position oor p to the OCOX group with a haloalkylating agent such as formaldehyde (for a formaldehyde donor) plus hydrogen halide in the presence of a haloalkylating catalyst such as a Lewis acid catalyst. That this reaction is feasible is surprising in three respects: (1) firstly, the halomethylation of phenols has generally not been successful, except where the ring was substituted by bulky or electronegative substituents; (2) secondly, the carbonyl group present in the haloformate side chain would be expected to be deactivating to a Lewis acid catalyst, by complexing therewith and (3) thirdly, assuming the Lewis acid catalyst could be made to function, the OCOX group would be expected to participate in the reaction (this group being known to acylate aromatic rings under Friedel-Crafts reaction condition) resulting in polymer formation. Surprisingly, the halomethylation of phenyl haloformates is found to proceed smoothly and under mild conditions.

The formaldehyde may be used as anhydrous monomer, trimmer or polymer, or in the form of its reaction products with hydrogen halide, and/0r CH OH, namely, halomethyl methyl ether or bis(chloromethyl) ether. In the case of these ethers, no additional hydrogen halide is required, although further hydrogen halide helps to produce improved yields. Suitable chloromethylating catalysts include Lewis acids, such as zinc chloride, boron trichloride, boron trifluoride, antimony chlorides, aluminum chloride, ferric chloride, tin tetrachloride, titanium chloride and other Lewis acid metal chlorides. Cocatalysts such as thionyl chloride are also helpful in some cases. Amounts from about 0.1 percent up to two molar equivalents of catalysts are used, the lower amounts where the ring is more reactive (such as where it bears several alkyl groups), the larger amounts where the ring is less reactive (such as where it bears halogen substituents). The quantity will also depend on the strength of the catalyst chosen (ZnCl SnCl SbCl relatively most active) and the temperature chosen (less catalyst needed at higher temperature).

The chloromethylation is conducted preferably in the liquid phase at 60 degrees to degrees. No solvent is required, but inert solvents may be used. Suitable solvents include aliphatic hydrocarbons, ethylene dichloride, methylene chloride, chloroform, benzene, dichlorobenzenes, nitromethane, other nitroalkanes, ethyl ether, and any other which are resistant to the reactants and catalyst. Other lower aldehydes such as acetaldehyde, propionaldehyde, and the like may be substituted for the formaldehyde to obtain the corresponding l-chloroalkyl side chains on the phenyl ring. Likewise, hydrogen bromide may be substituted for hydrogen chloride, thus obtaining bromomethyl groups in the product.

The carbamate compounds of the invention may be prepared by reacting the novel haloformates of the present invention of the formula:

where X, X A, m, n, p, q, b, and c are as defined above, and X" is a halogen chosen from bromine and chlorine,

with an amine of the formula HNZZ where Z and Z are as above defined. It is surprising andune'xpected that the reaction proceeds with the clean-cut selective replacement of X" rather than of both X and X", particularly since the chloroformate group is relatively sluggish in regard to chloride displacement compared to ordinary acid chloride. It is preferred that the reaction be conducted in the liquid phase at -60 degrees to +170 degrees centigrade, preferab y 40 degrees to '+150 degrees, using an acceptor of HCl which may be one extra molar equivalent of HNZZ or another base such as trialkylamine, pyridine, other tertiary amine, sodium carbonate, equeous caustic soda or potash, or the like. While a solvent is not necessary, it is convenient to employ a solvent, for example, an aliphatic hydrocarbon, such as benzene, toluene, mineral spirits, hexane, and the like, a chlorocarbon such as ethylene dichloride, chlorobenzene, perchloroethylene, and the like, an ether such as ethyl ether, dioxane, tetrahydrofuran, anisole, and the like, a nitrohydrocarbon such as nitrobenzene and the like, a ketone, such as acetone, methyl ethyl ketone, and the like, or another solvent, such as acetonitrile, dimethylformamide, and others. It has also been found that water may conveniently be employed where the HNZZ component is water soluble; generally, the haloformate reactant is not water soluble and a two-phase reaction mixture results,

in which the haloformate reacts with the HNZZ rather than undergoing hydrolysis.

When water is used as solvent for the HNZZ reactant, one of the other solvents such as those named above may be used as solvent for the haloformate. The HCl acceptor may be conveniently chosen to be a water-insoluble one such as caustic soda or potash, which have the advantage of low cost. These reactions are very rapid, and are generally complete in from 1 minute to one day; the limiting factor in the rapidity with which they can be run is often the rate at which the heat of reaction can be removed to hold the temperature at the desired level.

The product may be isolated by filtration or by distilling off of the solvent. Generally, the by product salt of the HCl acceptor can be filtered off or washed out with water.

The novel carbonates of the invention are represented by the formula:

wherein the substituent R is selected from the group consisting of alkyl, preferably of one to six carbon atoms, and halo-substituted alkyl, such as chloro-substituted alkyl or bromo-substituted alkyl, and the remaining substituents:

X and X are halogens of atomic weight between 34 and 81;

m is from 1 to 20;

q is equal to the remaining number of valences on the radical C H X n is from 1 to 2 p is from 1 to 5;

A is an alkyl radical, preferably of from 1 to about 6 carbon atoms;

C is from 0 to (5-p-b), inclusive; and

b is from 0 to (5-p), inclusive. In order that those skilled in the art may better understand the present invention, the manner in which it may be practiced, the following specific examples are given.

In the specification, examples and claims, all parts given are parts by weight and all temperatures are in degrees centigrade, unless otherwise specified.

1 0 EXAMPLE 1 a-Chloro-o-cres yl Chloroformate To parts of o-crseyl chloroformate, 1.4 parts of phosphorus trichloride and 0.1 part of benzamide, stirred at 118 to 120 degrees centigrade and exposed to the radiation from a mercury vapor lamp, is added a solution of 0.8 part of benzoyl peroxide in 80 parts of sulfuryl chlo ride. The addition is carried out over 1.2 hours. The reaction mixture is then factionally distilled to obtain 42 parts of a foreshot consisting principally of unreacted o cresyl chloroform-ate and a main fraction of 63 parts of colorless liquid boiling at 60 to 65 degrees centigrade, at 0.1 millimeter pressure absolute. The infrared spectrum of the material made, a-chloro-o-cresyl chloroformate, exhibited a band at 5.60 microns, indicating an acid chloride carbonyl.

Analysis.Calculated for C H O Cl Cl (total), 34.6; C1 (hydrolyzable by KOH/alcohol), 34.6. Found: Cl (total), 34.7; C1 (hydrolyzable by KOH/alcohol), 34.7.

EXAMPLE 2 a,a-Dichloro-o-cresyl Chloroformate To a stirred mixture of 70 parts of o-cresyl chloroformate and 1.4 parts of phosphorus trichloride was added 05 part of benzoyl peroxide in 112 parts of sulfuryl chloride at 118 to degrees centigrade over a period of three hours. Then, when the reaction evolving HCl and S0 had subsided, the reaction vessel was illuminated by a mercury vapor lamp and a further 83.4 parts of sulfuryl chloride were added. The reaction mixture was found to have increased in weight by 23 parts (theory, 24 parts for dichlorination). The product was then distilled to obtain the desired 0:,tz-di6hl0IO-O-CICSY1 chloroformate as a colorless liquid boiling at 84 to 86 degrees (0.1 millimeter) and having the correct total and hydrolyzable chlorine content.

EXAMPLE 3 a,a-Dibromo-o-cresyl Bromoformate In the same manner as Example 2, o-cresyl bromoformate and elemental bromine, employed in the place of ocresyl chloroformate and sulfuryl chloride, result in ot,adibromo-o-cresyl bromoformate.

EXAMPLE 4 a,a,a-Trichloro-o-cresyl Chloroformate Chlorine gas was passed into a mixture of 50 parts of o-cresyl chloroformate, 1.2 parts of phosphorus trichloride, 0.2 part of benzamide, and 0.5 part of benzoyl peroxide at to degrees, until no further hydrogen chloride evolution was observed. The product was then distilled toobtain 48 parts of colorless oil boiling at 82 to 92 degrees centiglade (0.08 millimeter). The infrared spectrum showed bands characteristic of ortho-disubstitution, indicating that none of the chlorine had attached to the benzene ring.

lAnalysis.Calculated for C H O Cl CI 57.5. Found: C 57.3.

. Preparation of an N-methylcarbamate derivative (described hereinafter) yielded a crystalline product C H O NCI the chlorine content of which was entirely hydrolyzable by KOH in refluxing ethanol.

EXAMPLES 5-19 The following examples were conducted according to the methods of Examples 1-4 above. In each case, a slight (5-20 percent) excess of halogenating agent was used relative to the number of halogen atoms to be introduced. The products were isolated by distillation and in most instances under vacuum, the boiling points of the products being listed below. j

Chlorl- Analysis, percent chlorine Ex. nating Temp., Time No. Haloiormate reactant (wt.) agent 0. (hrs) Product Boiling point, C. Calcd. Found Found b nr-Cresyl chloroiormate SOzCIz 135-140 5 a-iChlorg-m-cresyl chloro- 79-81.5 (0.1 mm.) 34.6 34.7 34.7

orma e. 6 "do 50:01: 138-140 6 a,a-Diohloro-m-cresyl chloro- 103-108) (0.25 44. 5 44. 4 43. 1

mm o. mm. 7 p-Cresyl chloroformate S0201; 135-142 5 a-Chloro-p-cresyl chloro- 76-82 (0.1 mm.) 34.6 34.6 34.6

iormate. M.P. 61-2 (recryst. from heptane). 8 "do S0101; 135-145 7 agi-DlfillOIO-p-GIGSY].0111010- 85-86 (0.1 mm.) 44.5 43.3 orma c. 9 "do S0201; 130-140 8% a,a,a-TI1'Oh10r0-p-cresy1 92-94 (0.04 mm.) 51. 8 50. 8 50. 8

chloroformate. M.P. 48-49.5. 10 3,5-xy1enyl chloroformate S0201; 138-140 4 a-1h1ord-3,5-xy1enyl chloro- 84-89 (0.1 mm.). 32.5 33.3 32.4

orma e. 11 do SOzCIz 138-140 9 a,a-Dichl0ro-3,5-xyleny1 105-110 (0.09 42. 0 40. 7 40. 8

chloroiormate. mm. 12.; d0 SOzClz 138-140 12 (2,0:,a-Trichloro-3,5-xylenyl 134-136 (0.15 49.3 49.6 49.6

chloroiormate. mm. 13 do SOzClz 136-140 16 a,a,a,a'-Tetrachloro-3,5- 138.5-140 (0.05 55.1 55. 4 55.2

xylenyl chloroformate. mm.) 14...--- 2,3-xylenyl ehloroformate SOzCln 130-180 5 a. fChlogo-ZB-xylenyl chloro- 90-95 (0.15 mm.). 32.4 32. 0

orma e. d0 S0201: 130-180 10 a,a-Dichloro-2,3-xylenyl 105-110 42. 0 41. 3

chloroformate. (0.1 mm.) 16..-" 3,4-xylenyl chloroiormate S0201: 130-180 5 a-Cfhloto3,4-xylenyl chloro- 90-93 05 32.4 32. 0

orma 8. 17 do S0101: 130-180 10 a,u.'-DlChl0!O3,4-Xyleny1 121-125 42. 0 41. 9

chloroiormate. (0.15 mm.). 18 3,5-diis0propyl phenyl 011 145-150 a-Chloro-3,5-diisopropylphenyl 81-82 22. 9 22. 8

chloroiormate. chloroiorrnate. (0.0 mm.)

2-(2,3-dichloropropyl) phenyl 115-117 39. 8 39. 8

chloroformate, (0. mm.) 19 2-ally1phenyl chloroformate.-- 01 d -20 and 2-(l,2,3-triohlor0propyl) phenyl 126-130 46. 8 46. 1

ehloroiormate. (0.1-0.2 mm.).

a Total. b Hydrolyzable by KOH/alc. LB. shows o-disubstitution pattern and absence of aliphatic G=G bond. 9 First 2 G1, then -140.

In a manner similar to Examples 5 to 19 the corre- EXAMPLE 22 sponding bromo analogs are prepared by utilizing bromine in the place of chlorine gas or SO CI EXAMPLE 20 Preparation of u,4-Dichloro-o-cresyl Chloroformate To 13 parts of 4-chloro-o-cresyl chloroformate were slowly added 13.5 parts of sulfuryl chloride under illumination by a mercury vapor lamp at 130-140 over two hours. The product was then distilled to obtain 9 parts of colorless liquid, boiling point 82-86 (0.15 millimeter).

Analysis.-Calculated for C H O C1 Cl (hydrolyzable by KOH/alcohol), 29.6. Found: Cl (hydrolyzable by KO-H/alcohol), 30.3.

In a similar manner, a,3,4,-tetrachloro-o-cresyl chloroformate and a,a,3,4,6-pentachloro-o-cresyl chloroformate were prepared by chlorination of 3,4,6-trichloro-o-cresyl chloroformate-at 135-175. Similarly, a,wu',u',2,4-hexachloro-3,5-xylcnyl chloroformate was prepared by chlorination of 2,4-dichloro-3,5-xylenyl chloroformate.

Chlorination of o-Cresyl Chloroformate in Absence of Catalysts and Inhibitors To 50 parts of o-cresyl chloroformate at 80 were added several parts of sulfuryl chloride. =No hydrogen chloride evolution was noted. The temperature was raised to 115 causing evolution of hydrogen chloride. LAt 115- '11'8, the gradual addition of sulfurylchloride was continued, until after 11 hours, a total of 44.4 parts of sul- -fury1 chloride was added. The product was then freed of volatile materials by briefly applying vacuum, e.'g., for 1 to 5 minutes. The residual chloroformate product was a .liquid containing both ring and side chain monochlorinated o-cresyl chloroformate.

Analysis.-Calculated for oc-ChlOl'O o cresyl chloroformate: Cl (total), 34.6. C1 (hydrolyzable by KOH/ alcohol), 3'4.6. Calculated for ring-chloro-o-cresyl chloroformate: Cl (total), 34.6; C1 (hydrolyzable by K0 H/ alcohol),(17.3. Found: Cl (total), 32.6. C1 (hydrolyzable by KOH/alcohol), 26.8.

Chloromethylation of Phenyl Chloroformate Into a stirred mixture of "156 parts of phenyl chloroformate, 39 parts of paraformaldehyde, 50 parts of po'wdered zinc chloride, and 500 parts of chloroform, was passed anhydrous hydrogen chloride at 55-60 for 8 hours. Then, the reaction mixture was added to ice water, stirred and the organic layer taken 011 and dried over magnesium sulfate. It was then filtered, the solvent was evaporated, and the residual liquid was distilled to obtain 40 parts of product, boiling point 84-92 (0J1 millimeter). The colorless distillate crystallized on standing and was recrystallized from a benzene-heptane mixture to obtain colorless crystals, melting point 60-615". This was found by infrared comparison to be the same compound as produced by a-monochlorination of p-cresyl chloroformate.

Analysis.-'-Calculated for C H O Cl Cl (total), 34.6; C1 (hydrolyzable by KOH/ alcohol), 34.5.

The bulk of the other material collected in the above distillation consisted of lower-boiling unreacted phenyl chloroformate, which was recycled to the next chloromethylation batch.

EXAMPLE 23 Chloromethylation of 3,5-Xylenyl Chloroformate Into a stirred mixture of 37 parts of 3,5-xyleny1 chloroformate, 7-8 parts of paraformaldehyde, 10 parts of pow dered anhydrous zinc chloride, and 150 parts of chloroform at 20-30 degrees, was passed hydrogen chloride gas over 10 /2 hours. The paraformaldehyde slowly dissolved. Then the reaction mixture was agitated briefly with ice water, after which the organic layer was decanted, dried over magnesium sulfate, filtered, and solvent was evaporated oif. The residual liquid was distilled .to obtain 17 parts of chloromethyl-3,S-dimethylphenyl chloroformate, boiling point -85 degrees (0.005 millimeter), in which the position of the chloromethyl group is indicated to be mostly para by NMR analysis.

Analysis.Calculated for C H O CI Found: CI 30.2.

13 In the same manner, pcresyl chloroformate is chloromethylated to produce 2-'(chloromethyl)-p-cresyl chloroformate, 2,3,5,6 tetramethylphenyl chloroformate is chloromethylated to produce 4-chloromethyl-2,3,5,6-tetramethylphenyl chloroformate, and 2 cyclopentylphenyl philes. The molecular weight of this product is increased by further reacting with disodium bisphenol-A, preferably in a co-solvent such as dioxane.

IEXAMPLE 27 chloroformate is chloromethylated to produce 4-chloro- [Preparation of polycarbonate polyether Resin methyl-2-cyclopentylphenyl chloroformate. I m 1 m I The haioalkylphenyl chloroformates of the invention f mlxture of l f z h d dT f 'f gi 2 exhibit'pesticidal activity per se, especially as nematocides, one mo 6 6 P Sat 0 SP eno fungicides and herbicides. 10 and 2,800 cc. of p-dtox-ane was stirred and the temperature of the reaction mixture was gradually raised to 100 EXAMPLE degrees until titration of an aliquot showed that all of ,Nematocidal Activity the chlorine had been released as sodium chloride. Then,

- the solution was filtered to remove salt and was con- 1 heavlly Infested i Melwdogyne l l centrated under vacuum, and it was added to a stirred acrim a Piant nlmatode specles Which mixture of 2,000 cc. of water and 2,000 cc. of benzene. Q 1 fhsease crops The benzene layer was then separated and evaporated to Poratcd c 10m f e obtain the desired product as a resin, capable of forming pou-nds P acre A {er F Waltmg peno transparent films. The infrared spectrum showed the prestomato seedlings were planted therein. Tomatoes were ence of carbonate linkages (band at 16 microns) and also planted in an adjacent unfumigated infested area. 20 etherlinkages One month later, the plants in the treated area were found The resultant resin is useful as the fihmfmming to be substantially free of root knots, whereas the plants ponent of electrically insulating coatings the untrgatgd s heavily damaged by root knots Analogous resins are produced by substitution of ozl q nemato 6 d b 2 3 1 1 chloro-mor -o-cresyl chloroforrnate for the p-isomer in at results were 0 tame wlt romo' the above procedure. Analogous resins prepared by use of ormate' EXAMPLE 25 ring polychlorinated or ring-brominated a-chloro-om-,

' or p-cresyl chloroformates are self-extinguishing when Herbicidal Activity ignited.

A heavy stand of roadside weeds (goldenrod and wild T zi i compomllis offthe mventllontare useful carrot, principally) was sprayed with a solution of a, a, i 2. 2 or g 'f g i many at a, 2,4 hexa'chloro 3,5 xylenyl chloroformate (4 o w 16 ex 1 1 pas a Proper 0 a 13 agree pounds) in kerosene 40 gallons). When examined one day EXAMPLE 28 later and three weeks later, substantially 100 percent kill was observed, whereas with the kerosene alone only a Preparation of cz-ChlOIO-O-CICSYI N-Methylcarbamate Pat -F foliage bum followed g Occurred- To 25 parts of ct-ChlOI'O-O-CIfiSYl chloroformate (Exam- The n9Y P of the mventl9n are useful also ple 1) in 40 parts of hexane was added 12.4 parts of methas polymer intermediates for preparation of polyethers ylamine in 100 parts of aqueous solution at 540 degrees and P Y -P carbonates- 40 with stirring. After 15 minutes, the precipitated solid was EXAMPLE 26 filtered out, washed with water, dried in air and recrystal- A lized from benzene-heptane mixture to obtain 20 parts of Conversion of gg giggggfz g gi to colorless crystalline solid, melting point 89-90 degrees y centigrade. The infrared spectrum showed the charac- .A 10 percent solution of a-chloro-o-cresyl chioroteristic NH band at 3 microns and the carbamate carbonyl formate in hexane and a 10 percent aqueous solution of band at 5.8 microns, sodium hydroxide were agitated vigorously, together at Analysis-Calculated for C H 0 NCl: Cl, 17.8; N, 20 degrees centigrade. In 15 minutes, a thick precipitate 70 Found; C1, 17.6; N, 7.0. of polymer had formed. After 30 minutes, the mixture X M had filtered and the solids washed with water and hexane. E PLE 29 Upon drying the solids, there was obtained a white solid Preparation of u-Bromo-o-cresyl-N-methylcarbamate polymer, insoluble in methanol, soluble in tetrahydro- The corresponding bromine compound was prepared furan. A film cast from tetrahydrofuran was clear, waterby utilizing wbromamcresfl bromoformate in place of white and non-tacky. The infrared spectrum shows a the wchlorwocresfl chloroformate strong band at 5.6 microns, characteristic of the .1' EXAMPLES 30-75 In a similar fashion, various of the side chain chlorillnkage- The Structure. P y believed to have nated alkylphenyl-chloroformates of the invention were carbonate and ether linkages in the chain, with terminal caused to react with various amines to obtain novel (halo- CH 'Cl groups capable of further reaction with nucleoalkyl)phenyl carbamates, as shown in the following Table.

Analysis Ex. Haloformate Amine Physical Empirical Cl 01 N N No. reactant reactant Product properties formula calcd. found calcd. found 30--.. a-Chloro-o-cresyl NH; a-Chloro-ocresyl Colorless crystals, CsHaO2NCl 7.5 7.2

chloroformate. carbamate. M.P. 119120 C.

31.... a, a-Dicbloro-o-cresyl CHaNHz a, a-Dichloro-o-cresyl Colorless crystals, CoHoOzNClz 30.3 29.4 5. 98 5. 94

chloroformate. N-rnethylcarbamate. M.P. IDS-110 C.

32.... a-Chloro-m-cresyl CHsNHz a-Chlorc-m-cresyl Colorless crystals, CoHmOzNCl 7.0 6.7

chloroformate. N -1nethylcarbamate. M.P. 84.5-" C.

33-.-- a,,x-Dichloro-m-cresyl CH3NH2 a, a-Dichloro-m-cresyl Syrup 7 CVHQOZNCIQ 30.3 28.7 5. 98 5.68

chloroformate. N-methylcarbamate. (undistillable).

34...- a-Chloro-p-cresyl CHaNHz a-Chloro-p-cresyl Colorless crystals, CsHwOzNCl 7.0 6.7

- chlorol'onnate. N -methylcarbamate. M.P. 131-3 C. 35---. a, a-Dlchloro-p-cresyl CHzNH; a, a-Dichloro-p-cresyl Colorless crystals, CnHnOzNClz 5.98 5.70

chloroformate. N-methylcarbamate. M.P. 95.597 C. 36-... a-Chlor0-3,5-xylenyl CHaNHz a-Chloro-3,5-xylenyl Colorless crystals, CwHrzOzNCl 16.6 17.3 6. 56 6.96

chloroformate. N-mcthylcarbamate. M.P. -95. 5 C. 37.... a,a-Dichloro-3,5- CHaNHz m,a-Dichloro-3,5-xylenyl Colorless crystals, CmHuOzNCla 28.6 28.0 5.64 5. 40

- xylenyl chloroformate. N-methylcarbamate. M.P. 12 122 C.

TABLEContinued Analysis Ex. Haloformate Amine Physical Empirical Cl Cl N N No. reactant reactant Product properties formula calcd. found 1 caled. found 38- a,a,a-Trichloro-3,5- CHaNHz. a,a,a-Trlchlro-3,5- Colorless crystals, 0 mHmOzN Ola 4. 96 4. 90

xylenyl ehloroformate. xylgnyl IgI-methyl- M.P. 81.583 0.

car ama e. 39..... u,a,a',n'-T9tl'a0h10r0- CHaNHz a,i1,o., a.-Tetrach1oro- Colorless crystals, CwHoOzNCh 44. 6 44. 0 4. 43 4. 26 3,5-xylenyl chloro- 3,5-xylenyl N-methyl- M.P. ll0l13 O. formate. carbarnate. 40.--.. u.-Ch1OIO-3,5-d1l$0- CHaNHz a-Chloro-3,5-diisopropyl- Undistillable CuHzoOgNCl 5.20 4.

propylphenyl chlorophenyl N-methylcartan syrup. iorrnate. bamate. 41..... a,u.-d1ch10r0-3,4 n-Butylamine-.. a,o.-Di0h10r0-3,4-Xyl9l1l Syrup CnHnOzNCh 4. 83 4. 90

xylenyl chloroiormate. N-n-butylcarbamate. 42 0. (CH3):CHNH-. a,a-Dichloro-3,4-xylenyl -d0 CnHrsOzNCl-z 5. 07 5. 2

N-isopropylcarbamate. 43 ..d0 M01pholine.--- a,a-Dichloro-3,4-xylenyl do C1aH15OaNClz 4. 60 4. 8

niorpholine-l-carboxyk a e. 44 ..do Cyelohexyla, a-Diehloro-3,4-xylenyl M.P. 108-9 CuaHmOzN C11 4. 52 4. 9

amino. N -cyelohexyl carbamate. 45... d0 Azindine u,a-Dichloro-3,4-xylenyl Syrup CnHuOzNCl: 5. 38 5.3

I (+EtaN). aziridine-l-carboxylate. 46..-" a, a. -Dl0h101'0-2,3- NHz a,a-Dichl0ro-2,3-xy1enyl M.P. 126-8 CDHQOZN C12 5. 98 5. 6

xylenyl chloroformate. carbamate. 47 d0 Cyclohexylu,a-Diehloro-2,3-xylenyl M.P. 1168 G H OZNCI; 4.52 4.1

' N-cyclohexylcarbamate.

n,u-I )lchloro-2,3-xyleny1 Solid, decomposes CnHuOzNClz 5. 38 p 5. 2

aziridine'l-carboxylate. on heating. 49 a, a'-Dl0h10!0-3,5- NHa a, a-Dichr0-3,5-xylenyl M.P. 134-4? CaHcOzNClg 30. 3 29. 4 5. 98 5. 3

xylenyl chloroformate. carbamate. 50 -.d0 (CHmOHNHL a,a-Dichloro-3,5-xylenyl M.P. 8l3 CX2H1502NC1I 25. 7 24. 9 5. 07 4. 8

N -isopropylcarbamate. 51 ..d0 Cyclohexyla,a-Dichloro-3,5-xylenyl M.P. 1035 C1 H nO NCla 22.9 22. 0 4.52 4.4

amine. N-cyclohexylearbamate. 52 ..do Di-n-butyla,v.-Dichloro-3,5-xylenyl Syrup CflHflOZNOl] 20. 8 21. 0 4.09 3. 8

amine. N,N-di-n-butylcarbamate. 53 .-d0 Aziridine a, e-Dichl0r03,5-xy1eny1 Solid decomposes C11Hl202NCh 36. 4 36. 0

(no EtsN). N-(Hhloroethyl) on heating.

cnrbamate. 54 do Morpholine. u,a'-Dichloro-3,5-xyleny1 Syrup C 3H 5O3ClzN 23.3 22. 5 4. 4. 34

norpholine-l-carboxyla e. 55..... a-(lhloro-o-cresyl Aniline a-ChlOIO-MIQSYI N M.P. 94-6" 0 CuHnClNOz 13. 6 13. 1 5. 37 5. 37

phenylcarbamate. 56...-. a-Chloro-o-cresyl m-Chloroa-(lhloroto-cresyl N-m- M.P. 8486 C"-.- OuHnClz z 0 9 72 64 chloroformate. aniline. chlorophenyl carbamate. 57 do p-Chloroa-ChlOIO-O-GTGSYI N-p- M.P. 113-15 CuHnCIzNO: 24. 0 23. 9 4. 2 4. 59

aniline. chlorophenyl carbamate. 58 do 3,4-dichloroa-Ghloro-o-cresyl N-3,4- M.P. 109111 C.-- CuHmClgNOz 32.3 32.0 4. 24 4. 02

aniline. dichlorophenylcarbamate. 59 ..do Dimethyl a-Chloro-o-cresyl N,N- Oil CmHuClNOz 16. 6 16. 3 6. 57 6. 48

amine. dimethylcarbamate. 60 a-Chloro-m-cresyl Aniline q-Ohloro-m-cresyl N- M.P. 123-6 0--...- CuHnClNOz 13. 6 13.9 5.37 5. 29

chloroiormate. phenylcarbamate. 61 do m-Chloroa-Chloro-m-cresyl N-m- M.P. -71.5 C CuHuChNOz 24. 0 23- 9 72 4- 63 aniline. chlorophenyl carbamate. 62 -.do p-Chloroa-Chloro-m-cresyl N-p- M.P. 132-3 0"... O H CIZNO: 24. 0 23. 8 4. 72 4. 48

aniline. chlorophenylcarbamate. 63 ..do 3,4-dichloroa-Chloro-m-cresyl N- M.P. -111 C-.- CMHIBCIQNOI 32.3 31.7 4.24 3. 98

aniline. 3,4-dichlorophenyl carbamate. 64 do Dimethyl a-Chloro-m-cresyl N,N- Oil CNHHCINOQ 15. 6 16. 2 6. 57 5. 73

amine. dimethylcarbamate. 65. a-ChlOl'O-D-OIGSYI Aniline a-Ghloro-p-cresyl N- M.P. 132-3 C14H12C1N02 18. 6 13. 2 5. 37 5. 22

chloroiormate. phenyl earbamate. 66 do m-Chloroa-Chloro-p-cresyl N-m- M.P. 1134 C.-. C H chNog 24.0 23. 7 4. 72 4. 49

aniline. ehlgrophenyl carbuma e. 67 do p-Chloroa-Chloro-p-cresyl N-p- M.P. 1569 C..-. CHHnChNO, 24. 0 22.5 4.72 4. 71

aniline. chlgrophenyl carbuma e. 68 do 3,4-di-chloro a-Chloro-p-cresyl N3,4- M.P. 115.5-117"-.- C H Cl NO 32. 3 25. 0 4.24 2. 63

aniline. dicltilorophenylcarbama e. 69 d0 Dimethyla-Chloro-pcresyl N,N- M.P. 6869.5 C..- CmHmClNOz 16. 6 16. 4 6. 57 7. 10

amine. dimethyl carbamate. 70. 2-(2,3-diehloropropyl) CHaNHz 2-(2,3+iichloropropyl) Syrup (undistill- CnHmClzNO: 27. 1 29. 0 5. 35 4. 74

phenyl chloroformate. p yl t y a 1B ma e. 71-..- a-Chloro-2,3-xylenyl CHaNH: a-Ohl0r0-2,3-xylenyl N- M.P. 72-254 (iso- ONH OZNCI 6.65 7.0

ohloroformate. methyl carbamate. mer mixture). 72.- a,a-Dich10ro-2,3- CHaNHz a,a-Dichl0ro-2,3-xylenyl M.P. 138-9". C H OZNCI 28. 6 28. 6

xylenyl chloroformate. N-methy fi 1 73. a-Chloro 3,4-xylenyl CHzNHz a-Ch10ro3A-xylenyl N M.P. 83-6" C HHO NCI 6. 55 6. 3

chloroformate. methylcarbamate. 74 -Dichl0m 3,4 -zy1anyI CH NH a,a-Dichloro-3,4-xylenyl M.P. 7- CioHuOzNCI 3- 6 5 ohlorolorrnate. N-methy amat 75- Chloromethyl-3,5- CHaNHz Chloromethyl-3,5-xylenyl M.P. 78-110" (ism CnHuO NCl 15. 6 16. 2

xylenyl chloroiormate. N-methyl carbamate. mer mixture) 1 Hydrolyzable by KOH/alo.

The haloalkylphenyl carbamates derived from the haloalkylphenyl chloroformates of the invention are useful as cidal activity, whereas placing two halogen atoms on the benzene ring practially destroys such activity.

EXAMPLE 76 Bean plants infested with black bean aphids were sprayed with 0.1 percent aqueous dispersions of a-chloroo-cresyl N methylcarbamate, a,a-dichl0ro-m-cresyl N- 17 methylcarbamate, and a,a-dichloro-o-cresyl N-methylcarbamate. After two days, 100 percent mortality of the aphids was observed in each case.

EXAMPLE 77 Third instar larvae of the Mexican bean beetle were placed on bean plants with 0.1 percent aqueous disperions of a-chloro-3,5-xylenyl N-methylcarbamate, 2-(2,3-dichloropropyl) phenyl N-methylcarbamate, and 2-(1,2,3- trichloropropyl) phenyl N-methylcarbamate. After two days, 60. percent kill was observed with the first compound and 100 percent kill with the second and third compounds.

The carbamates derived from the haloalkylphenyl chloroformates of the invention are also useful as herbicides, especially the N-aryl, N-chloroalkyl, N-higher (alkyl), N,N-dialkyl, N-cycloalkyl, N,N-ethylene (i.e., aziridinyl-l-carboxylates), and N,N-3-oxapentamethylene (i.e., morpholine-l-carboxylates), as well as, in general, those carbamates having ring halogen in addition to side chain halogen, as shown in Example 97 below.

The a-haloalkylphenyl carbamates, carbonates and the parent phenols derived from the a-haloalkylphenyl haloformates of the invention also may be converted to further useful pesticides by nucleophilic displacement of the a-halogen which exhibits a high degree of reactivity. In this manner, the utility of the novel a-haloalkyl haloformates of the invention encompasses the use of these new compounds in an extremely broad range of useful conversions to valuable products, as shown in the following examples.

EXAMPLE 78 Preparation of u-(Diethoxyphosphinyl)-o-cresyl N-Methylcarbamate A mixture of 1 part each of ot-ChlOIO-O-CIESYI N-methylcarbamate and triethyl phosphite was heated at 100 degrees for 9 /2 hours, during which time one molar equivalent of ethyl chloride was liberated. The reaction mixture was then evaporated at 100 degrees under 0.25 mm. pressure to remove unreacted phosphite, leaving the desired phosphonate as a colorless clear syrup.

Analysis.-Calcd. for C H O NP: P, 10.3; N, 4.6; CI, 0.0. Found: P, 9.64; N, 4.2; Cl, 0.1.

EXAMPLE 79 a-Dimethoxyphosphinyl-o-cresyl N-Methylcarbamate The product, from a-chloro-o-cresyl N-methylcarbamate and excess trimethyl phosphite reacted at 100 degrees as in the preceding example, is a light tan syrup.

Analysis.--Calcd. for C H O NP: P, 11.0. Found: P, 12.0 (undistilled crude).

By conducting the reaction at 140 degrees, methyl isocyanate is lost and the free a-dimethyloxyphosophinyl-ocresol is obtained.

In a similar manner to Examples 78 and 79 the same phosphonate compounds were prepared by utilizing the a-bromo-o-cresyl N-methylcarbamate in place of the u-chloro-o-cresyl N-methylcarbamate.

EXAMPLE 80 a-(Di-n-butoxyphosphinyl)-0-cresol and u-(Din-n- Butoxyphosphinyl)-o-cresyl N-methyl carbamate The initial product, made by heating parts of achloro-o-cresyl N-methylcarbamate and parts of trin-butyl phosphite at 130-135 degrees, is a light tan oil which is found to have lost the N-methylcarbamate group and is established by infrared (OH band) and phosphorus analysis to be the free phenol, a-(di-n-butoxyphosphinyl)- o-cresol.

Analysis.-Calcd. for C H O P: P, 10.3. Found: P, 10.8.

To this phenol was added a molar excess of methyl isocyanate and a trace of dibutyl tin laurate catalyst.

After standing 10 hours, the excess isocyanate was removed at 0.15 mm. vacuum leaving the desired N-methylcarbamate as a clear light tan oil having the correct nitrogen analysis.

In a like manner, the following are made:

a-dimethoxyphosphinyl-m-cresol and the corresponding N-methylcarbamate (from u-chloro-m-cresyl N-methylcarbamate and trirnethyl phosphite),

a-diethoxyphosphinyl-p-cresol and the corresponding N- methylcarbamate (from oz-ChlOI'O-P-CIGSYI N-methylcarbamate and triethyl phosphite),

a-dimethoxyphosphinyl-,5-xylenol and the corresponding N-methylcarbarnate (from a-chloro-3,5-xylenyl N- methylcarbamate and trimethyl phosphite),

a ar-bis(diethoxyphosphinyl)-2,4-, 2,5-, 3,4- and 2,5-xylenol and the corresponding 'N-methylcarbamates (from u,u'-dichloro-2,4-, 3,5-, 3,4- and 2,5-xylenyl N-methylcarbamates and triethyl phosphite),

a di(heptadecyloxy) phosphinylpseudocumenol and the corresponding N-methylcarbamate (from a-chloro pseudocumenyl N-methylcarbamate and methyl di- (heptadecyl) phosphite).

These side chain phosphonate-substituted phenols are useful as flame retardant co-monomers in phenolic resins. Furthermore, the carbamates derived from them have pesticidal properties.

EXAMPLE 81 Bean plants infested with black bean aphids were sprayed with 0.1 percent aqueous dispersions of a-(dimethoxyphosphinyl)-o-cresyl =N-methylcarbamate, and u-(diethoxyphosphinyl)-o-cresyl N-methylcarbamate. In 48 hours, 92 percent and 100 percent aphid mortality, respectively, was observed.

Further examples of nucleophilic displacements of a-haloalkylphenyl N-methylcarbama'tes derived from the haloformates of the invention include displacements by anions of the RX- type, where R'is a hydrocarbyl or acyl group and X is oxygen or sulfur. These reactions are general for virtually any RX nucleophile, and are illustrated by the following few examples. The products of these reactions show valuable pesticidal activity.

EXAMPLE 82 u-Acetoxy-o-cresyl N-Methylcarbamate A mixture of 4.2 parts of sodium acetate and 10 parts of a-chloro-o-cresyl chloroformate in parts of glacial acetic acid is heated at degrees for 2 days. The acetic acid was stripped under reduced pressure, the residue taken up in benzene, washed with water, and evaporated to 100 degrees (0.1 mm.) to obtain 8 parts of a-acetoxy-ocresyl N-methylcarbamate, a pale yellow syrup. The infrared spectrum shows two overlapping bands in the carbonyl region, indicative of the'ester and carbamate structures.

Analysis.Calcd. for C H O N: N, 6.3. Found: N, 6.7.

In a similar manner are produced a-isobutyroxy-ocresyl N-methylcarbamate (using sodium isobutyrate), u-benzoyloxy-o-cresyl N-methylcarbamate (using sodium benzoate). Analogously, a,a-diacetoxy-3,5-xylenyl N- methylcarbamate is produced from a,ot'-diChlOI'O-3,5-.

EXAMPLE 83 a-(N,N-Dimethylthiocarbamylthio)-o-crcsy1 N-Methylcarbamate A mixture of 10 parts of a-chloro-o-cresyl N-inethylcarbamate and 18 parts of 40 percent aqueous sodium dimethyldithiocarbamate was stirred for 4 /2 hours at washed with water, dried and recrystallized from benzene to obtain 11 parts of colorless crystals, m.p. 147-8 degrees.

Ana lysis.Calcd. for C H O S N N, 9.86. Found: N, 9.56.

This compound, sprayed at the rate of 125 parts per million in aqueous dispersion onto bean plants infested with larvae of Mexican bean beetle, produced 100 percent beetle mortality in 2 days.

EXAMPLE 84 a-(N,N-Diethylthiocarbamylthio)-o-cresyl N-methylcarbamate The procedure of the preceding example was followed, employing 16.6 parts of 51.4 percent aqueous sodium diethyldithiocarbamate. The product was a colorless crystallizing solid, m.p. 59-60 degrees Centigrade.

- Analysis.Calcd. for C H N S N, 8.97. Found: N, 8.78.

In an analogous manner, a-chloro-o-cresyl N-methylcarbamate was converted to a-(N-methylthiocarbamylthio)-o-cresyl N-methylcarbamate (by reaction with sodium N-methyldithiocarbamate), to a-(N,N-dibutyllthiocarbamylthio)-o-cresyl N-methylcarbamate (by reaction with sodium N,N-dibutyldithiocarbamate) and to a-(N,N-dipropylcarbamylthio) o cresyl N-methylcarbamate (by reaction with potassium N,N-dipropylthiolcarbamate). Likewise a-chloro-3,5-xylenyl N-methylcarbamate was converted to u-(N,N-diethylthiocarbamylthio)-3,5-xylenyl N-methylcarbamate (by reaction with sodium diethyldithiocarbamate). The thiocarbamate compounds thus produced are pesticidally active.

' In addition to insecticidal activity, these compounds exhibit fungicidal, germicidal, and plant growth regulatory properties.

EXAMPLE 85 u-Thiocyano-o-cresyl N-methylcarbamate A mixture of parts of a-chloro-o-cresyl N-methylcarbamate and 4.05 parts of sodium thiocyanate in 200 parts of ethanol was stirred for 15 hours, filtered with clay and charcoal to remove salt, the solvent evaporated, and the residue recrystallized from carbon tetrachloride to obtain 4 parts of colorless crystals, m.p. 77-78 degrees Centigrade. The infrared spectrum established that the carbamate structure was present (NH at 3.03 microns, 0:0 at 5.85 microns) as well as the SCN group (C=N at 4.68 microns).

. Analysis.-Calcd. for C H O N S: N, 12.60. Found: N, 12.61.

This compound admixed with nematode-infested soil at 147 pounds per acre, substantially prevented nematode-caused root damage on cucumber seedlings planted in this soil. The same compound applied to soil at 64 pounds per acre killed aphids on bean seedlings planted in the treated soil, thus exhibiting systemic action.

In a similar manner, a-thiocyano-3,5-xylenyl N-methylcarbamate, a colorlem solid, m.p. 90-1 degrees, was prepared from a-chloro-3,5-xylenyl N-methylcarbamate. Similarly, 'a,u'-dithiocyano 3,5 xylenyl N-methylcarbamate was made from a,a-dichloro-3,5-xylenyl N- methylcarbamate and a,ot'-dithiocyano-2,3-xylenyl N- methylcarbamate from the corresponding dichloro compound. Similarly, using sodium cyanide or cuprous cyanide in place of thiocyanate, the analogous a-cyano compounds were made. For example, a-cyano-o-cresyl N-methylcarbamate was prepared from a-chloro-o-cresyl N-methylcarbamate and CuCN.

By reaction of the u-haloalkylphenyl esters described above with nucleophiles of the RS- or R0 type where R is acyl or hydrocarbyl, a large number of valuable pesticides may be made.

20 EXAMPLE 86 u- (Diethoxythiophosphinylthio -o-cre syl N- Methylcarbamate A mixture of 10 parts of a-chloro-o-cresyl N-methylcarbamate and 15 parts of sodium 0,0-diethylphosphorodithiolate in parts of methyl ethyl ketone is held at 35-50 degrees Centigrade for 6 days. The solution is then washed with water and aqueous sodium bicarbonate, dried over magnesium sulfate, filtered and stripped to degrees (0.2 mm.) leaving the product as 15.5 parts of pale tan syrup.

Analysis.Calcd. for C H O NS P: N, 4.42. Found: N, 4.52.

This compound, sprayed at 0.1 percent in aqueous dispersion onto nasturtium infested with two-spotted mites, produced 100 percent mortality of mites in 24 hours, as well as ovicidal effects as shown by the failure of mites to hatch from eggs present at the time of spraying.

In an analogous manner are produced a-(dimethoxythiophosphinylthio)-3,5- and 3,4-xylenyl N-methylcarbamate from a-chloro-3,5- and a-chloro-3,4-xylenyl N- methylcarbamate and sodium 0,0-dimethylphosphorodithiolate; similarly, a-(diisopropoxythiophosphinylthio)-ocresyl N,N-dimethylcarbamate is prepared from a-ChlOI'O- o-cresyl N,N-dimethylcarbamate and sodium 0,0-diisopropylphosphorodithiolate.

EXAMPLE 87 a-Methoxy-o-cresyl N-methylcarbamate To 10 parts of oc-ChlOI'O-O-CIGSYI N-methylcarbamate in 100 parts of methanol was added 2.7 parts of sodium methylate in 200 parts of methanol at 25 degrees Centigrade. Volhard titration showed that the theoretical amount of sodium chloride had been formed. After 15 hours, the solvent was evaporated. The product was found by infrared and nitrogen analysis to be a mixture of 'a-methoxy-o-cresyl N-methylcarbamate and otmethoxy-o-cresol. To replace the lost N-methylcarbamate groups, 5 parts of methyl isocyanate plus 0.01 part of dibutyltin laurate catalyst was added, the mixture let stand overnight, and stripped free of isocyanate at degrees and 0.1 mm., leaving the desired carbamate as a light tan syrup.

Analysis.Calcd. for C H ON: N, 7.18. Found: N, 7.01. I

In an analogous manner, a-(2-methoxyethoxy)-ocresyl N-methylcarbamate and a-(2-methoxyethoxy-ocresol were prepared from a-chloro-o-cresyl N-methyl carbamate and sodium 2-methoxyethoxide, a-furfuryloxyo-cresyl N-methylcarbamate and a-furfuryloxy-o-cresol were prepared from u-chloro-o-cresyl N-methylcarbamate and sodium furfuroxide. a-Aryloxy phenols and carbamates therefrom are made analogously.

EXAMPLE 88 a- (2,4-Dichlorophenoxy)-o-cresol and N- Methylcarbamate A solution of 50 parts of a-chloro-o-cresyl N-methylcarbamate and 45 parts of sodium 2,4-dichlorophenate in 200 parts of methyl ethyl ketone was held at 40-50 degrees for 2 hours. The mixture was cooled, diluted with hexane, and filtered to obtain colorless crystals, m.p. 131.5-132 degrees Centigrade, showing the characteristic infrared carbamate bands.

Analysis.Calcd. for C H O NCl N, 4.29. Found: N, 4.26.

Upon heating of the carbamate at degrees Centigrade in the presence of 0.1 percent dibutyltin laurate catalyst and passing of a slow nitrogen stream through the melt to sweep out the evolved methyl isocyanate, the above carbamate was caused to revert to the parent at- (2,4-dichlorophenoxy) o cresol, a colorless solid, neutralization equivalent (potentiometric titration by 21 tetrabutylammonium hydroxide in puridine solution) 269 mg./milliequivalent.

- In an analogous manner, a-chloro-o-cresyl N-methylcarbamate is converted to a-phenoxy-o-cresyl N-methylcarbamate (by reaction with sodium phenoxide), to a-(4- nitrophenoxy)-o-cresyl N-methylcarbamate (by reaction with sodium p-nitrophenoxide), to lX-(2,4 dinitrophenoxy)-o-cresyl N-methylcarbamate (by reaction with sodium 2,4-dinitrophenoxide), to a-(2,4,5-trichlorophenoxy)-o-cresyl N-methylcarbamate (by reaction with our aureus at 0.001 percent concentration in a nutrient agar. Furthermore, a-(N-loweralkylamino)-o-cresyl N- methylcarbamates can be acylated to highly insecticidal a- (N-loweralkyl-N-acylamino-o-cresyl N-methylcarbamates.

Another group of useful pesticidal derivatives which are rendered synthetically accessible via the novel haloalkylphenylchloroformates of the invention are the haloalkylphenyl alkyl or aryl carbonates, i.e., unsymmetrical esters of carbonic acid, one esterifying moiety being the haoalkylphenyl group. In general these may be prepared 10 sodium 2,4,5-tr1chlorophenox1de), and to a-pentachloroby reaction of an alcohol or an alcoholate with the desired phenoxy)-o-cresyl N-methylcarbamate (by reaction with haloalkylphenyl chloroformate. The thiol analogs may be potassium pentachlorophenate). Similarly, a-cl11oro-3,5- prepared analogously, using mercaptides as reactants. xylenyl N-methylcarbamate is converted to a-phenoxy-3,5- xylenyl N-methylcarbamate by reaction with sodium 15 EXAMPLE 9 phenoxide. Similarly a,4-dichloro-o-cresyl N,N-dimethyl- A mixture of parts of a,u'-dichloro-3,4-xylenyl chlocarbamate 1S converted to .a-(2,4-d1ch1orophenoxy)-4- roformate and 40 parts of methanol were admixed. A mild chloro-o-cresyl N,N-dimethylcarbamate (by reaction with spontaneous exotherm occurred. After hours, the mixpotassium 2,4-dichlorophenox1de). ture was distilled free of unreacted alcohol and hydro- The a-hydrocarbyloxyalkylphenyl carbamates thus pregen chloride by applying a vacuum (ultimately 0.2 mm.) pared are pest1c1dally active. For example, houseflies and raising the temperature gradually to 100 degrees. The dipped in a 0.1 percent aqueous dispersion of a-phenoxyproduct was obtained as a residual light yellowish oil. o-cresyl N-methylcarbamate showed 100 percent mor- Analysis.-Calcd. for C H O Cl Cl, 28.5. Found: tality in 24 hours. Cl, 28.6.

Furthermore, the tat-haloalkylphenylhaloformates of In the same manner, the following carbonates were the invention can be converted to tit-haloalkylphenyl esters made. In every case the product was a liquid.

Percent chlorine Chloroformate used Alcohol used Carbonate made Theory Found a-Chloro-o-cresyl- Eth annl Ethyl-ot-ChlOlO-O-GIBSYL 16. 5 16. 4 Isopronannl Isopropyl-a-chloro-o-oresyl 15. 5 15. 3 DO n-Bntannl n-Butyl-a-chloro-o-cresyL 14. 6 14. 1 Do- 2-Methoxyethanol Z-Methoxyethyl-a-ehloro-o-cresyl 14.4 14.5 D n-Am n-Amyl-achlcro-o-cresyl l3. 8 13. 4 a,a'-Dlehloro-3,5-xylenyl Methanol Methyl-a,a-dichloro-3,5-xylenyl.- 28.5 28.4 D0 Ethanol Ethyl-0:, a'-dich10I0-3, 5-xylenyl. 27. 0 27. 0 Do Isopropanol Isopropyl-a,a-dichloro-3,5-xylenyl 25.6 26.0 Do. Z-Methoxyethanol 2-Methoxyethyl-a, a-dich1oro-3,5-xy1eny 24.2 23. 6 D -Bnmnnl n-Butyl a, a'-dlChl0lO-3, 5-xylenyl 24. 4 23. 7 D0- n-AmyL n-Amyl a, a-dichloro-3, fi-xylenyl- 23. 5 23. 3 Do Ethyl mercaptan. S-ethyl a, cl-dichloro-3, 5-xylenyl Do. Z-ChlomethanoL. 2-Chloroethyl-a,a-dichloro3,5-xylenyl 35.7 35.0 a, a, a-Trlchloro-3, 5-xylenyl- Methanol. Methyl a, a, a'-l3lichl010-3, 5-xylenyL.-. 37. 5 34. 2 a, a, a, nl-Tetrachloro-ES, fi-xylenyl .-do Methyl a, a, a, a-tetrachloro-3, 5-xyleny 44. 6 44. 9 a-Chloro-o-cresyl- 2-Chloroethano 2-Chloroethyl a-ehloro-o-cresyl 28. 5 27. 0

l Thlolcarbonate.

EXAMPLE 89 N-(o-Hydroxybenzyl)pyridinium Chloride N'- Methylcarbamate A solution of 10 parts of u-chloro-dcresyl N-methylcarbamate and 3.9 parts of pyridine in parts of ethanol is allowed to stand for 6 days at 30-50 degrees Centigrade, until Volhard titration indicates that the theoretical amount of chloride ion is evolved. The solution was then evaporated to 100 degrees (10 mm.) leaving 12.3 parts of a viscous water soluble syrup having the theoretical percent nitrogen and ionic chloride.

In an analogous manner, a-ChIOI'O-O-OI'CSYI N-methylcarbamate and trirnethylamine (20 percent alcoholic solution) yield a-trimethylammonio-o-cresyl N-methylcarbamate chloride, a-bromo-p-cresyl N,N-dimethylcarbamate and triethylamine yield a-triethylammonio-p-cresyl N,N- dimethylcarbamate bromide, a,2,4-trichloro-o-cresyl N- (3,4-.dichlorophenyl) carbamate and dimethylamine yield et-dimethylamino-2,4-dichloro-o-cresyl N (3,4 dichlorophenyl) carbamate, a,a'-dichloro-3,5-xylenyl N-methylcarbamate and aniline yield a, x-dianilino-3,S-xylenyl N- methyl carbamate, a-chloro-o-cresyl N-methylcarbamate and N,N-dimethyl-N-laurylamine yield u-N,N-dimethyl- N-laurylammonio-o-cresyl N'-methylcarbamate chloride, to cite a few illustrative examples. These compounds are pesticidal. The last named quaternary ammonium compound and its N-higher alkyl homologs are strong germicides, producing inhibition of the growth of Staphyllococ- In a similar manner the following ring-halogenated sidechain halogenated aryl carbonates were made:

1 In presence of 1 molar equivalent of triethylamine, in dioxane solvent.

These carbonates were found to be useful inter alia as herbicides. For example, methyl a',2,4-trichloro-o-cresyl carbonate applied in aqueous dispersion at the rate of 8 pounds per acre to crabgrass seedlings produced percent mortality in 1 week. Isopropyl a,a,a,a,2,4-hexachlo-' ro-3,5-xylenyl carbonate sprayed in aqueous dispersion at the rate of 8 pounds per acre to a mixed population of ragweed and pigweed produced complete kill in 10 days.

Another group of useful insecticidal derivatives which can be prepared from the novel haloalkylphenyl chloroformates of the invention are the phosphorothioates of the structure Aryl-OCOSPS(Oalkyl) wherein the aryl residue is that derived from the haloalkylphenyl chloroformate. Since the side-chain halogen is reactive, it may be further displaced 'by a second SPS(Oalkyl) group. Both of these classes of derivatives exhibit useful insecticidal properties. 1

23 EXAMPLE 91 Preparation of Unsymmetrical Thioanhydride of oz-ChlO- ro-o-cresyl Carbonic Acid and 0,0-dimethylphosphorodithioic Acid A mixture of 10.25 parts of a-chloro-o-cresyl chloroformate and 9 parts of sodium 0,0-dimethylphosphorodithioate in 20 parts of methyl ethyl ketone was allowed to warm spontaneously to 35 degrees, let stand 10 hours, filtered to remove salt, and evaporated to remove solvent, leaving the product as a reddish oil. The infrared spectrum showed a carbonyl band at 5.72 establishing that the COCl function had reacted and that a new carbonyl structure had formed.

Analysis.-Calcd. for C H O S PCl: P, 9.99. Found: 9.88.

This product, sprayed at 0.1 percent in aqueous dispersion onto black bean aphids produced 95 percent aphid mortality in 48 hours.

In a like manner,

and p-(CH O) PS-SCH C H OCO-SPS(OCH are prepared from a,0L,Ot-t1'lCh1OI'O-p-CI'6Sy1 chloroformate to ot-bromo-p-cresyl chloroformate and one or two molar equivalents, respectively, of sodium '0,0-dimethyl phosphorodithiolate.

The u,u'-dichloro-2,3-xylenyl and a,oc'-dichl0rO-3,4-Xylenyl chloroformates have the special advantage of permitting conversion to valuable heterocyclic systems not otherwise readily obtainable. For instance, they may be converted to a,u'-dichloro-2,3- and -3,4-xylenyl carbamates or other esters which then may be reacted with ammonia or primary amines to form dihydroisoindolyl esters, or with aqueous bases to form phthalanols or phthalanyl esters, or with sulfide anion to form thiophthalanols or thiophthalanyl esters (dihydroisothianathenols or dihydroisothianaphthenyl esters). The N-methylcarbamates of these heterocyclic phenols are highly insecticidal and also nematocidal.

EXAMPLE 92 1,3-Dihydroisothianaphthen-4-yl N-Methylcarbamate A solution of 10 parts of a,a'-dichloro-2,3-xylenyl N- methylcarbamate and 5.5 parts of 60 percent sodium sulfide (commercial flaked hydrate) in 200 parts ethyl alcohol was stirred 15 hours at 30-33 degrees, then an aliquot was titrated for chloride, which showed all the available a-chlorine to have been released as chloride ion. The mixture was filtered, evaporated to dryness, and the residue examined by infrared. It was found to contain 1,3-dihydroisothianaphthenol (H band) as well as the carbamate (C=O band). Therefore the residue was dissolved in tetrahydrofuran, treated with 5 parts of methyl isocyanate, re-evaporated and recrystallized from benzene-methanol to obtain the desired N-methylcarbamate as a colorless solid, m.p. 1157 degrees.

Analysis.Calcd. for C I-I O NS: N, 6.7, S, 15.3. Found: N, 6.5, S, 15.5.

This compound, sprayed at 0.1 percent in aqueous dispersion on larvae of the Mexican bean beetle, produced 100 percent insect mortality in 48 hours.

EXAMPLE 93 1,3-Dihydroisothianaphthen-5-yl N-Methylcarbamate A procedure identical to the preceding example was used to convert a,u'-dichloro-3,4-xylenyl N-methylcarbamate. The product, recrystallized from aqueous methanol, was a colorless solid, mp. 133-5 degrees.

Analysis.Calcd. for C H O NS: N, 6.7. Found: N, 6.4.

This compound as well as the isomer of the preceding example when admixed with nematode-infested soil at 147 pounds per acre gave complete prevention of nematode-caused root knotting of cucumber seedlings planted in the treated soil.

The acid halides of the invention are also useful as chemical intermediates for the synthesis of side-chain halogenated phenols not otherwise accessible. For example, careful hydrolysis of a,a-dichloro-o-, m-, or p-cresyl chloroformate by adding one molar equivalent of water (conveniently in a co-solvent such as dioxane) at 0 degrees to 60 degrees yields oz,oc-diChl0rO-O-, m-, or p-cresol all hitherto unknown; a,a,a-tlichlOl'0-O-, m-, or p-cresyl chloroformate on hydrolysis yields similarly mega-trichloroo, m-, or p-cresol all hitherto unknown; a-chlorom-cresyl chloroformate similarly on careful hydrolysis yields a-ChlOI'O-l'Il-CIGSOI, hitherto unknown. Such side,- chain halogenated phenols have only existed before in the form of their esters which however cannot be hydrolyzed to the phenols themselves without destruction of the labile haloalkyl side chain.

More extensive hydrolysis of the compounds of the invention yields phenols substituted with HOCH O=CH, and HOC(=O) groups. While many of these are known, the route to them via the compounds of the invention is in many cases more economical than the synthetic methods of the prior art. Thus u,a-dichloro-ocresyl chloroformate may be hydrolyzed to salicylaldehyde, a useful perfume ingredient, and a,oz,a-tfiChl0r0-0- cresyl chloroformate may be hydrolyzed to salicylic acid, a useful drug.

EXAMPLE 94 Chloromethylation of 3,5-Xylenyl chloroformate Into a stirred mixture of 37 parts of 3,5-xylenyl chloroformate, 78 parts of paraformaldehyde, 10 parts of powdered anhydrous zinc chloride, and 150 parts of chloroform at 2030 degrees Centigrade, was passed hydrogen chloride gas over 10 hours. The paraformaldehyde slowly dissolved. Then the reaction mixture was agitated briefly with ice water, after which the organic layer was decanted, dried over magnesium sulfate, filtered, and solvent was evaporated olf. The residual liquid was distilled to obtain 17 parts of chloromethyl-3,S-dimethylphenyl chloroformate, b.p. 80-85 degrees (0.005 mm.) in which the position of the chloromethyl group is indicated to be mostly para.

Analysis.-Calcd. for C H 0 Cl CI, 30.4. Found: Cl, 30.2.

In the same manner, pcresyl chloroformate is chloromethylated to produce 2-(chloromethyl)-p-cresyl chloroformate, 2,3,5,6 tetramethylphenyl chloroformate is chloromethylated to produce 4-chloromethyl-2,3,5,6-tet ramethylphenyl chloroformate, and arcyclopentylphenyl chloroformate is chloromethylated to produce 4-chloromethyl-2-cyclopentylphenyl chloroformate.

EXAMPLE Nematocidal Use caused root knots, which were found to be substantially. absent. By contrast, similar seedlings grown in the in-' fested soil wtihout the nematocidal treatment exhibited roots which were all heavily damaged by nematode-caused root knots;

25 EXAMPLE 96 I Activity on Houseflies Adult houseflies (Musca domestica) were treated with 0.1 percent aqueous dispersions of various of the N-methylcarbamate compounds of the invention and various known carbamates. The percentage knockdown at 2 hours and percentage kill at 24 hours were as follows:

2 -hour 24-hour N-methylcarbamate knockdown ll 1!,E-Diflh10l'O-M1'GSY1 100 100 a,a-Diehloro-m-eresyl 100 100 2 (2,3 dichloropropyl)phenyl 100 100 2-(l,2,3trichlor0propyl)phen l 95 100 -Cresyl 80 $0 85 5 EXAMPLE 97 Herbicidal Activity EXAMPLE 98 Bacteriostatic Activity These carbamates, especially the N-arylcarbamates, are also active antibacterial compounds. A nutrient agar was admixed with 100 parts per million by weight of various of the carbamates of the invention and then inoculated with spores of Staphylococcus aureus. The growth or absence of growth of bacterial colonies was noted in three days. The chemicals thus tested are shown in the table below:

Degree of In- Chemical hibition a,ot,a'. trichloro-o-cresyl N-(p-chlorophenyl)carbamate a,a-dichloro o cresyl N-(p-nitrophenyl)carbamate ot,ot,ot trichloro-o-cresyl N-(3,4-dichlorophenyl) carbamate u,a,4-trichloro o cresyl N-(p-chlorophenyl) carbamate ot-chloro-2-isopropylphenyl N-phenylcarbamate u,a,4,6-tetrachloro o cresyl N-l-naphthylcarbamate a-chloro-p-cresyl N-methylcarbamate i p-cresyl N-methylcarbamate Key: :growth largely prevented, i :border line action, .-=no inhibition.

While there have been described various embodiments of the invention, the methods and elements described are not intended to be understood as limiting the scope of the invention, as it is realized that changes'therewith are possible, and it is further intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the invention broadly in whatever form its principle may be utilized.

26.1 What is claimed is: 1. A halogenated carbamate of the formula:

wherein the substituents (a) X and X are halogens of atomic weight from 34 to (b) m is an integer from 1 to 20;

(c) p is an integer from 1 to 5;

(d) b is an integer from 0 to 5-));

(e) c is an integer from 0 to 5-p-b;

(f) n is an integer from 1 to 2 (g) q is thenumber of remaining valences of the m q n p;

(h) A is an alkyl substituent containing l-6 carbon atoms;

(i) Z and Z are radicals independently selected from the group consisting of hydrogen, phenyl, mono: and dihalogenated phenyl, nitrophenyl and l-naphthyl groups, with the proviso that at most one of the radicals Z, and Z may be hydrogen.

2. A halogenated carbamate of the formula:

tcmmxap wherein the substituents (a) X and X are halogens of atomic weight from 34 (b) m is an integer from 1 to 20;

(c) p is an integer from 1 to 2;

(d) b is an integer from 0 to 5-p;

(e) c is an integer from 0 to 5-p-b and c is zero where more than one halogen is attached to any one carbon atom of the C H X group;

(f) n is an integer from 1 to 4;

(g) q is the ;number of remaining valences of the C H X group;

(h) A is an alkyl substituent containing l-6 carbo atoms;

(i) Z and Z' are radicals independently selected from the group consisting of hydrogen, phenyl, monoand di-halogenated phenyl, nitrophenyl and l-naphthyl groups, with the proviso that at most one of the radicals Z and Z may be hydrogen.

3. The compound of the formula oiN 4. The compound of the formula 5. The eompound of the formula 6. The compound of the formula Cl: C

0 elk-1w 28 7. The compound of the formula 15 JAMES A. PATTEN, Primary Examiner PC1-1050 STATES PATENT OFFICE n Y 569 CERTIFICATE OF CORRECTION Patefit NO- 3.825.582 I D t July 23. 197k Inventor-(s) v Edward D. [Weil It is certified that error appears in the aboveidentified patent I and that said Letters Patent are hereby corrected as shown below:

' Column 1, line 24, after 3,651,129", insert --issued March 21, 1972" line 28, "makng" should read --making--. Column 2, line 11, "38" should read "34". 7 Column 3, line 64, 'n'hydrocarboyl" should read --hydrocarbyl--. Column 4, second row of benzene rings from bottom of column, first benzene ringon left that part of the formula reading CL- -OCOCl should read v "1 c1 cucl last row of rings on bottom of column, first benzene 'ring on left reading c1 OCOCl should read 0Com C]. CHC12 Cl CHClZ Cl Cl Column 7, lines &-5, that part of the formula reading 0 should O OCY read OCY 7 Column 8, line 31, "trimmer" should read --trimer--. Column 9,, line 12, "equeous" should read --aqueous--; line 32, "water insoluble" should read --water-soluble--; line 64, "2 should read "a -+1. umns 15 and 16 Example 56 under product "-(-Ghloro:o-

cli'esyl I should read =(-Chloro-6cresyl-- Example 74, under Haloformate reactant '-,dichloro-3,4-zyleny1 should read ,,;:'-dichloro-3,4- y y I UNITED STATES PATENT OFF ICE CERTIFICATE OF CORRECTION Page 2 Patent No. 3,815,582 Dated July 23, 1974 R ve -1013( Edward D. Weil It is certified that: error appears in the above-identified patent and that said Letrers Patent are hereby corrected as shown below:

I" Column 17, line 6, "disperions" should read --di spersions-- line 62, "s(-(Din-'-n-" should read o(-'(Di-n- Column .22, under Percent chlorine Found "44.9" should read "44.0"; and "27.0" should read --27.9--. Column 24, line 73, "wtihout" should read --without--. I

Signed and sealed this 28th day of January 1975. V

(SEAL) Attest: v

MCCOY M. GIBSON-JR. c. MARSHALL DANN Arresting Officer o Commissloner of Patents 

